Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 19925 - 19931
Published: Aug. 29, 2023
We
report
the
development
and
characterization
of
a
library
Ir(III)
photocatalysts
capable
undergoing
spin-forbidden
excitation
(SFE)
under
orange
light
irradiation
(595
nm).
These
catalysts
were
successfully
applied
to
construction
synthetically
valuable
C(sp2)-C(sp3)
bonds
inaccessible
with
existing
methods
low-energy
light-driven
dual
nickel/photoredox
catalysis,
demonstrating
synthetic
utility
this
photocatalyst
family.
The
are
accessing
both
oxidatively
reductively
activated
coupling
partners,
illustrated
through
deaminative
arylation
potassium
alkyl
trifluoroborate
cross-coupling
reactions
aryl
halides.
demonstrate
diverse
substrate
scopes
paradigms
mild
conditions
in
first
example
metallaphotoredox
coupling.
Journal of the American Chemical Society,
Journal Year:
2025,
Volume and Issue:
unknown
Published: Feb. 5, 2025
Despite
a
well-established
and
growing
body
of
work
on
nickel(0)
precatalysts,
the
potential
complexes
as
bifunctional
precatalysts
remains
underexplored.
In
this
study,
we
synthesized,
characterized,
evaluated
catalytic
activity
(Ni(0)(DQ)dtbbpy),
bifunctional,
red-light-sensitive,
air-stable
complex.
Owing
to
its
unique
photophysical
properties,
it
effectively
catalyzed
etherification
amination
aryl
bromides
under
620–630
nm
light
irradiation,
functioning
both
photocatalyst
an
active
metal
catalyst.
Mechanistic
studies
density
functional
theory
(DFT)
calculations
further
confirmed
exceptional
absorption
properties
Ni(0)(DQ)dtbbpy
in
red-light
region,
well
electron
transfer
process
triggered
by
irradiation.
ACS Catalysis,
Journal Year:
2022,
Volume and Issue:
12(24), P. 15590 - 15599
Published: Dec. 5, 2022
Easy,
efficient,
and
economic
synthesis
of
anilines
remains
an
important
challenge
in
synthetic
chemistry.
In
this
study,
a
Ni(OAc)2-bipyridine
complex
is
shown
to
readily
catalyze
the
amination
aryl
halides
with
ammonium
salts
under
direct
excitation
light,
allowing
broad
array
chlorides
bromides
be
converted
into
corresponding
primary
(hetero)arylamines
absence
external
photosensitizer.
Late-stage
modification
drug
molecules
15N-labeling
amines
are
also
demonstrated
number
examples.
Photoinduced
generation
Ni(I)-bipyridine
species
believed
key
step
reaction,
enabling
Ni(I)/Ni(III)
cycle
for
catalytic
turnover.
Journal of the American Chemical Society,
Journal Year:
2022,
Volume and Issue:
144(33), P. 15372 - 15382
Published: Aug. 15, 2022
The
Ni/Ir-photocatalyzed
coupling
of
an
aryl
bromide
(ArBr)
with
alkyl
(RBr)
has
been
analyzed
using
in
situ
LED-19F
NMR
spectroscopy.
Four
components
(light,
[ArBr],
[Ni],
[Ir])
are
found
to
control
the
rate
ArBr
consumption,
but
not
product
selectivity,
while
two
([(TMS)3SiH],
[RBr])
independently
rate.
A
major
resting
state
nickel
identified
as
ArNiII(L)Br,
and
13C-isotopic
entrainment
is
used
show
that
complex
undergoes
Ir-photocatalyzed
conversion
products
(Ar-R,
Ar-H,
Ar-solvent)
competition
release
ArBr.
range
competing
absorption
quenching
effects
lead
correlations
between
Ir
Ni
catalyst
loadings
reaction
Differences
Ir/Ni
Beer-Lambert
profiles
allow
be
increased
by
use
a
shorter-wavelength
light
source
without
compromising
selectivity.
minimal
kinetic
model
for
process
allows
simulation
provides
insights
optimization
these
processes
laboratory.
Journal of the American Chemical Society,
Journal Year:
2023,
Volume and Issue:
145(36), P. 19925 - 19931
Published: Aug. 29, 2023
We
report
the
development
and
characterization
of
a
library
Ir(III)
photocatalysts
capable
undergoing
spin-forbidden
excitation
(SFE)
under
orange
light
irradiation
(595
nm).
These
catalysts
were
successfully
applied
to
construction
synthetically
valuable
C(sp2)-C(sp3)
bonds
inaccessible
with
existing
methods
low-energy
light-driven
dual
nickel/photoredox
catalysis,
demonstrating
synthetic
utility
this
photocatalyst
family.
The
are
accessing
both
oxidatively
reductively
activated
coupling
partners,
illustrated
through
deaminative
arylation
potassium
alkyl
trifluoroborate
cross-coupling
reactions
aryl
halides.
demonstrate
diverse
substrate
scopes
paradigms
mild
conditions
in
first
example
metallaphotoredox
coupling.
